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Thermokinetic Investigation of Binary Cu/Zn Hydroxycarbonates As Precursors for Cu/Zno Catalysts

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Thermokinetic Investigation of Binary Cu/Zn Hydroxycarbonates As Precursors for Cu/Zno Catalysts Thermokinetic investigation of binary Cu/Zn hydroxycarbonates as precursors for Cu/ZnO catalysts Andrey Tarasov, Julia Schumann, Frank Girgsdies, Nygil Thomas and Malte Behrens Fritz Haber Institute of the Max-Planck Gesellschaft, Department of Inorganic Chemistry, Faradayweg 4-6, 14195 Berlin (Germany) Fax: (+49)30-8413-4401 [email protected] Keywords: Thermogravimetry, Cu/Zn hydroxycarbonates, decomposition kinetics Abstract A combination of thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) coupled to mass spectrometry has been applied to study the thermal decomposition of Cu/Zn hydroxycarbonates, which are used as a precursor for the active methanol synthesis catalyst. Original TG and DSC profiles and results of a formal kinetic analysis of the calcination process are compared with transformations occurring in the solid phase, which has been studied by means of in-situ XRD. A series of hydroxycarbonate precursors with different Cu/Zn molar ratios (40/60, 60/40, 80/20) was synthesized under conditions reported as optimum for catalytic performance. The samples contain primarily two crystalline phases, aurichalcite (Cu,Zn)5(CO3)2(OH)6 and zincian malachite (Cu,Zn)2CO3(OH)2. At least four formal decomposition stages of CO2 and H2O evolution cause the major mass loss in the TG experiments. The best-fit quality for the all studied samples was obtained for a four-step competitive reaction model. The experimental TG dependences are adequately described by the n-th order equation and 3D Jander diffusion equation. The effects of the gas flow, sample mass, and water transfer conditions on the reaction pathway were studied. The presence of H2O vapor in the reaction feed accelerates the decomposition and dramatically changes the reaction TG profile. The decomposition enthalpy of mixed Cu/Zn (80/20) hydroxycarbonate was determined, and the formation enthalpy of the decomposition intermediate, a carbonate-modified oxide, was 0 calculated to be ΔHf =-633.7±5.6 kJ/mol. 1. Introduction Recently, there has been a growing interest in the methanol synthesis and steam reforming of methanol reactions. Part of this interest stems from the projected methanol economy [1] and the increasing need for non-fossil fuels. Methanol can be used as a fuel in combustion engines and in methanol fuel cells or as a source of hydrogen for PEM fuel cells. It is also an important 1 feedstock for the synthesis of a variety of fine and bulk chemicals. Today, methanol is one of the top ten petrochemicals. Ternary Cu/ZnO/Al2O3 systems are widely used in industry as catalysts for methanol synthesis and low-temperature water-gas shift reaction. The synthesis of such systems consists of a multi-step preparation route involving coprecipitation of mixed Cu/Zn hydroxyl-carbonate precursors, calcinations of these precursors to give a mixture of oxides and reduction of the CuO component. A vast number of studies on this system have shown that experimental conditions of each step significantly affect the microstructure, physicochemical properties and catalytic performance of Cu/ZnO/Al2O3 2, 3, 4, 5. However, different research groups have pointed out that the thermal activation has a pronounced effect on the porosity and structure of Cu-based catalysts. Reading and Dollimore [6] applied conventional rising-temperature thermogravimetry and introduced constant rate thermal analysis (CRTA) for examining the thermal decomposition of copper hydroxycarbonate. The development of the surface area as a function of the extent of decomposition was found to be markedly non-linear. The CRTA technique was used later for careful study of the decomposition mechanism of Cu/Zn hydroxycarbonates with different Cu-to- Zn ratio [7]. At the same time, the number of publications focusing on the description of the decomposition process and the influence of calcination conditions on the catalytic activity is quite limited [8, 9, 10, 11]. Some studies [12, 13] deal with the characterization of binary precursors for Cu/ZnO catalysts, which serve as a suitable model for technical ternary Cu/ZnO/Al2O3 systems. Thermoanalytical studies often lack detailed information on reaction macrokinetics. To the best of our knowledge, the decomposition kinetics and dependence on reaction parameters, such as the mass of the precursor and gas-flow conditions, have not been reported for Cu/Zn hydroxycarbonates. The investigation of the decomposition kinetics provides better insight into transformations in the solid state upon heating and enables the optimization of the calcination protocol. These investigations help to design custom-made calcination protocols for individual samples, which in turn can be a determinative factor in catalytic activity. The current work is aimed at studying the decomposition process of Cu/Zn hydroxycarbonates by means of coupled TG, DSC and MS techniques. The description of thermal events and the overall picture of calcination with respect to changes occurring in the solid and gas phases are also given. In addition, we performed the formal kinetic analysis of the calcination process of the mixed Cu/Zn hydroxycarbonates under recommendations of ICTAC (International Confederation for Thermal Analysis and Calorimetry) [14]. The TG and DSC profiles of the decomposition and the results of a kinetic analysis of the calcination process are compared with transformations taking place in the solid phase, by means of in-situ XRD. 2. Experimental 2.1 Sample Preparation Cu/Zn precursors were prepared by pH-controlled coprecipitation [15] in an automated reactor (Mettler-Toledo LabMax). Different phases were prepared: aurichalcite (Cu:Zn, 40:60 molar ratio), zincian malachite (Cu:Zn, 80:20) and a phase mixture with a composition close to the industrially applied catalyst (Cu:Zn, 60:40). Appropriate amounts of Zn(NO3)2 6H2O and 2 Cu(NO3)2·3H2O were dissolved in Millipore water (0.09µS/cm) and 15 ml of concentrated HNO3 to obtain 600 ml of a 1 M solution of the metal salts. This solution was introduced into the reactor containing 400 ml of water at a constant rate of 20 ml/min. A 1.6 M Na2CO3 solution was automatically added to maintain constant pH 6.5. The precipitation temperature was 338 K. Precipitation was followed by ageing for 1 h (338K), after pH-drop. The solid was then filter- collected and washed several times by redispersion in water until the conductivity of the washing medium was below 0.5 mS/cm. The solid hydroxycarbonate precursors were obtained by spray drying. 2.2 XRD XRD data were collected using a STOE STADI P transmission diffractometer equipped with a primary focusing Ge monochromator (Cu Kα1 radiation) and a linear position-sensitive detector (moving mode, step size 0.5 , counting time 30 s/step). The samples were mounted in the form of a clamped sandwich of small amounts of the powder fixed with a small amount of grease between two layers of a thin polyacetate film. The phase composition was determined by full pattern refinement in the 2 range 4-80 according to the Rietveld method using the TOPAS software [16] and crystal structure data from the ICSD database. Summarized crystallographic parameters of phases, the original XRD patterns and the results of Rietveld refinement are presented in supplementary information. 2.3 TG-MS Simultaneous TG–DSC was carried out on a NETZSCH STA 449C Jupiter thermoanalyzer equipped with an electromagnetic microbalance with top loading. The TG resolution was 0.1µg. The relative error of mass determination was 0.5%. A highly sensitive sample carrier with Pt/Pt–Rh thermocouples was used. Measurements were taken in the temperature range 313–900K under a controlled Ar/O2 flow 79:21 ml/min at a heating rate of 2, 5, 10 K/min. Gases used in the experiments were Ar (99.999%) and O2 (99.999%). Samples of 10–15 mg were positioned into corundum crucibles (45 µl) without lids. Temperatures were calibrated against the melting points of In, Sn, Bi, Zn, Pb, Al and Au. The gases evolved in the thermal analyses were monitored with a quadrupole mass spectrometer (QMS200 Omnistar, Balzers) coupled to STA via a quartz capillary heated to 313K. The experiments were performed with an electron ionization energy of 60 eV and a dwell time per mass of 0.2s. The main mass gates used were m/e 18 (H2O), 28 (CO), 30 (NO), 32 (O2), 44 (CO2), and 46 (NO2). The experiments with sample loadings higher than 30 mg and with water vapor in the feed gas were performed on Rubotherm DynTherm Thermogravimetric Analyzer. The gas line was equipped with a saturator filled with water and held at room temperature. For better quality of DSC curves, calorimetric experiments were carried out on a Mettler-Toledo HP DSC 827 calorimeter, with Au-AuPd Sensor, in 40-µl aluminum crucibles in a dynamic synthetic air (70 ml/min). Temperatures were calibrated against the melting points of In and Zn. 3 2.4 Kinetic Analysis The kinetic data obtained in the experiments were processed using Netzsch software. The Proteus Thermal Analysis program was used for processing the raw TG and DSC curves, determining heats and mass changes, and smoothing and differentiating the curves. The integration of DSC heat effects was performed in the range of 400-720K, using tangential baseline. The Thermokinetics program was used for processing kinetic dependences and solving the direct and inverse kinetic problems. Eighteen different kinetic models were tested. For all models under consideration, a set of statistical criteria of adequacy was used according to the Netzsch procedure [17, 18]. The optimal model was selected on the basis of the discrepancies between the calculated and experimental values. The Peak Separation program was used for deconvolution of polymodal DSC peaks into components, processing TG curve derivatives, and searching for a best- fit function describing the peak shape. The reaction order parameter n was limited to a maximum value of 4±1.
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